Fungicidal compositions



United States Patent M 3,127,311 FUNGECEDAL 0MPOSETIONS Gtto Telle andFerdinand Grows, (Iolognetammheim,

Germany, assignors to Farbenfabriiren Bayer Aktiengesellseha'it,Leverlrusen, Germany, a corporation of Germany No Drawing. Filed lliar.8, 19st, Ser. No. 13,453 @iaims priority, application Germany Mar. 10,1959 d @laims. (62. 167-42) The present invention relates to and has asits objects new and useful compositions of organic fungicides, whichcontain in addition to known active fungicides certain specialemulsifiers and other adjectives which render the inventive compositionshighly active and especially stable. The special ingredients containedin the inventively improved fungicidal compositions are fatty alcoholpolyglycol ethers or fatty acid polyglycol esters, metal salts, specialmagnesium salts of fatty acids and lower aliphatic or aromaticpoly-basic carbonic acids or hydroxy carbonic acids.

The use of organic fungicides for combating of fungous diseasesespecially for culture purposes during the last years became ofincreased importance. Since the number of organic fungicides is limitedthere has been done a great amount of work in the formulating of thesefungicides to achieve thereby some effects which were not obtained bycompositions known as yet. One method to find new compositions was tocreate finely divided metal of microsized particles. This could beperformed by using special powder mills. Another method to obtaincompositions of organic fungicides with improved properties is the useof special detergents, emulsifiers, special inert materials and thelike. known fungicides by a special formulation is not only to improvethe activity, but also to broaden the time of activity and to give thecompositions more rapid actions. It is known that as yet many organicfungicides regarding their immediate activity as well as their acuteactivity come within the range of the activity of inorganic metalcompounds, especially coppcr fungicides. Sometimes they are even betterthan the latter. The disadvantage of organic fungicides regardingcompatible copper sprays, however, is the fact that the time of activityis much shorter than the time of activity of copper compounds. This maybe due to the reason that organic fungicides may be easier attacked bychemical influences than the extremely stable inorganic compounds.

It has been tried to improve the time of activity of organic fungicidesby adding special compounds including detergents, emulsifiers, and thelike. But as yet only very few formulations have been found which had animproved period of activity. Also some good compositions have beenproven to be of special advantage only for one compound and the samecomposition could not be used advantageously regarding other organicfungicides. The cause for this fact might be due to the differentmechanisms of action of the various organic fungicides. In the lattergroup there are as it is known two main classes of compounds. In oneclass the activity is due to the unchanged molecule, but otherfungicides only act by their decomposition products, which are formed byhydrolysis, oxidation and other reactions on the plants.

Some auxiliary agents in fungicidal compositions especially detergents,emulsifiers, hydrophobating agents, adhesives act on the time of actionand rapidity of action in a negative way. A theoretical example is thefollowing: If an organic fungicide which acts by its decompositionproducts is brought into stable formulations, the particles are coveredby water impenetrable layers and thereby the micro-particles are notable to be decomposed and there- The purpose of improving 3,127,311Patented Mar. 31, 1964 by they become inert or less biologically activeon the plant.

In accordance with the present invention it has now been found thatimproved compositions of organic fungicides, especially improvedfungicidal spray compositions broadly may be obtained, if as auxiliarysolvents fatty acid metal salts and fatty acid polyglycol esters orfatty alcohol polyglycol ethers or aryl-polyglycol ethers are used.Additionally a certain amount of a solid lower aliphatic diorpolycarboxylic acid or an aromatic carboxylic acid should be present inthe inventive fungicidal compositions. Compositions of the above saidtype not only have a highly acute activity (rapid action), but they alsorender the organic fungicides a long lasting activity. The compositionsof the present invention also secure a good distribution on the plants.A redistribution on the sprayed plant organs by rain water also does notlead to such an amount as this is the case with other known fungicidalcompositions.

The above mentioned polyglycol ethers may be an aryloxypolyglycol ethersuch as the reaction product of ethylene oxide or propylene oxide ormixtures thereof with phenol, the different cresols, and the like,hydroxy diphenyls (especially 0- or p-hydroxydiphenyl), with benzylhydroxydiphenyl, and the like. Especially advantageous are fatty alcoholpolyglycol ethers such as the reaction products of C to C alcoholsespecially C to C alcohols with ethylene oxide or propylene oxide ormixture thereof. Those reaction products are e.g. lauryl, stearyl,palmityl or oleyl polyglycol ethers. Under polyglycol ethers there is tobe understood a reaction product containing more than at least 2 glycolradicals in the molecule and usually not more than about glycolradicals. Most suitable are the commercially available polyglycol etherscontaining average between about 8 to 20 glycol radicals. The fatty acidglycerol esters as above mentioned should contain at least oneunesterified OH-group. As examples there may be mentioned the lauricacid-glycerol-monoand -diesters, the palmitic acid-glycerol-monoand-diesters, the stearic acid-glyceroldiester (Emocithin) and the like.Metal salts of fatty acids in the meaning of this invention areespecially salts of C to C carbonic acids and should contain as a saltforming metal especially an alkaline earth metal (magnesium, calcium andthe like), zinc, manganese, aluminium, iron, copper and the like.Especially useful organic acids are lauric, stearic, palmitic, margaric,oleic, linoleic acid and the like.

Especially suitable solid lower aliphatic dior polybasic acids which areuseful for the inventively used compositions are oxalic acid, maleicacid, succinic acid, adipic acid, malic acid, citric acid, and the like.Aromatic acids are especially phthalic acid, salicylic acid, and thelike.

Organic fungicides which may be formulated with the inventively usedcompositions are broadly the known compounds used in the field of plantprotection as yet. As examples there may be mentioned at first the wellknown thio-carbamates (TMTD=tetramethyl-thiuram disulfide, ferricdimethyl dithiocarbamate, manganese ethylene bis-dithiocarbamate,disodium ethylene bis-dithiocarbamate, zinc ethylenebis-dithiocarbamate, zinc dimethyl dithiocarbamate). Other examples areN-trichloromethyl mercaptoA-cyclohexene-l.Z-dicarboximide,2.3-dichloro-l.4-naphthoquinone, Z-heptadecyl glyoxalidine acetate,dinitro-( l-methyl heptyl)-phenyl-crotonate.

A special advantage of the inventively used combinations is the factthat this combination does not decrease the biological activity, butprotects the active compound against influences which ordinarily makethe active compound less efiicient. It has even been found that thebiological activity is greater than the activity of formulations ofknown constituents used as yet for practical purposes. A furtheradvantage is the increased period of activity of the inventively usedcompositions.

The inventive compositions usually contain the active ingredient in anamount of 5 to 95%, the balance being inert materials and theinventively used additional compounds. Usually the polyglycol ether orpolyglycol ester compound is present in an amount of 1 to 25% morespecifically 2 to 8%. The fatty acid salt in the inventively usedcompositions should be present in an amount of 1 to 15%, especially 2 to10%. The solid hydroxy carboxylic, dicarboxylic or polycarboxylic acidat last is present in an amount up to 10%, es ecially in an amount of 2to 8%. Inert materials used for the inventively described compositionsare talc, chalk, kaoline, bentonite, kieselguhr and especially finelydivided highly dispersable silicic acids in the form of their variouscommercially available brands.

The following examples are given to illustrate this invention without,however, restricting it in any way:

(l) TetramethyLthiuram-disulfide (TMTD):

(a) 80.0% of tetramethyl-thiuram-disulfide 4.3% of oleyl-polyglycolether 2.0% of magnesium stearate 6.0% of colloidal kaoline Rest finelydivided silicic acid (b) 80.0% of tetramethyl-thiuram-disulfide 3.0% ofoleyl-polyglycol other 1.0% of magnesium stearate 10.0% of adipic acidRest silitine Z (finely divided silicic acid, commercially available)60.0% of tetramethyl-thiuram-disulfide 8.0% of oleyl-polyglycolether15.0% of magnesium stearate 3.0% of finely divided silicic acid, andRest finely divided silicic acid (2) Zinc-ethylene-bis-dithiocarbamate(ZINEB):

(a) 80.0% of zinc-ethylene-bis-dithiocarbamate 4.5% of oleyl-polyglycolether 2.0% of magnesium stearate Rest finely divided silicic acid (11)60.0% of zinc-ethylene-bis-dithiocarbamate 4.0% of oleyl-polyglycolether 2.0% of magnesium stearate Rest finely divided silicic acid (c)80.0% of zinc-ethylene-bis-dithiocarbamate 3.0% of oleyl-polyglycolether 1.0% of magnesium stearate 8.0% of salicylic acid Rest finelydivided silicic acid (at) 60.0% of z nc-ethylene-bis-dithiocarbamate15.0% of magnesium stearate 10.0% of oleyl-polyglycol ether Rest finelydivided silicic acid (3) Zinc-dimethyl-dithiocarbamate (ZIRAM):

(a) 90.0% of zinc-dimethyl-dithiocarbamate 2.0% of magnesium stearate4.0% of oleyl-polyglycol ether Rest finely divided silicic acid1-chloro-2.4-dinitro-naphthaline (CDN): (a) 50.0% of1-chloro-2.4-dinitro-naphthaline .0% of magnesium stearate 5.0% ofoleyl-polyglycol ether 1.0% of naphthaline-sulfonate Rest finely dividedsilicic acid (b) 75.0% of 1-chloro-2.4-dinitr0-naphthaline 2.0% ofmagnesium stearate 4.0% of oleyl-polyglycol ether 2.0% of zinc oxideRest finely divided silicic acid are completely destroyed by the fungus.

(5) N trichloro methyl-thic-(dimethyl-arninosulfonicacid-anilide) (a)50.0% of N-trichloro-methyl-thio-(dimethylamino-sulfonic-acid-anilide)4.0% of oleyl-polyglycol other 1.0% of magnesium stearate 8.0% ofsalicylic acid Rest finely divided silicic acid 50.0% ofN-trichloro-methyl-thio-(dimethylamino sulfonic acid anilide) 10.0% ofmagnesium stearate 5.0% of decyl-polyglycol ether 8.0% of salicylic acidRest finely divided silicic acid An identical composition may beprepared from: N- tric-hloro-methyl mercapto4-cyclo-hexene-1.Z-di-carboximide.

In the following the superiority of the inventively used compositionsregarding their acute activity and resistance to rain leaching isdemonstrated with some organic protective fungicides on Phytophthorainfes-tans (late blight, tomatoes).

The following method has been adopted: in the green house young tomatoplants grown under standard conditions (soil, temperature, humidity andlight) are used after the 4 to 5 first leaves are formed. The plants arethen sprayed by normal means to running off with inventively usedcompositions in an aqueous dilution of the concentration shown in thetables below.

Thereafter they are placed for 24 hours in the green house to become dry(23 C.) (70 to relative humidity). Thereafter they are inoculated withzoospores of the fungus in bidistilled water. The plants then are placedfor 5 days in a humidity chamber at relative humidity and at atemperature of 18 .to 20 'C. The plants treated as well as theinoculated plants during incubation are randomized in the humiditychamber. After the test is terminated the non-treated check plants Theplants treated are evaluated by counting each leaf according to thedestruction, whereby 6 values are used. According to this standardmeasure number the evaluation number may be obtained and compared with anon-treated control which is set 100. The evaluation numbers in thetables below thus give infestation in percent of the check.

It tested for resistance to rain leaching the plants when the spray isdried are sprayed by a finely divided measure spray of distilled water,corresponding to a quantity of 10 mm. rain during 10 minutes, on aturning table. The

as described above.

The plants thus treated and the plants non-sprayed (or rained) areartificially infested The other procedure is by the method given above.

EXAMPLE 5 N-Tric/zlol'o-Methyl-Thio-(Dinlet/1ylamino-Sulfonic AcidAnilide) the same as described before. 5 Active Evaluation numberingredient l3 concc-ntra EXAMPL 1 tion, Un- SprayedTcti'amethyl-Thiul'am-D sulfide (TMTD) percent sprayed TEST ([0 Normalformulation (with emulsifier 0.025 7 31 only) 0.0125 2t 50 g t E 1 gg253; I; lngrc len va uaconcentration Imeunve combmanon g g numbNon-treated control 100 100 W l 0.025 25 e claim:

a a l r Y 1 Normnlformul non (commoremymal able) 8-852 1. Funglcldalcompositions containing an organic Inventive combination 010125 24fungicide in an amount from 5 to 95% together With Non-treated control100 (a) 2 to 10% of a member selected from the group consisting ofphenyl hydroxy polyglycol ethers, fatty TEST acid polyglycol esters andfatty alcohol polyglycol etllers, the fatty alcohols and acids having 8to Acme Evaluation number carbon atoms and being esterified Wlth up to50 glycol residues, and c sprayed 25 (b) 1 to 16% of fatty acid metalsalts, the fatty acid Percent sprayed having 8 to 25 carbon atoms andthe metal being a member selected from the group consisting of call f f(cllmmercmuy 8-83 55 cium, magnesium, zinc and aluminium, and

a {I a G V 1 0.0125 34 59 (0) up to 10% of a solid organic acid, thisacid being Inventive combmqfion 16 8-83 2 a member selected from thegroup consisting of a Q 010125 17 43 lower aliphatic dicarboxylic acid,a lower aliphatic Non'tmted comm 100 100 hydroxy-carboxylic acid andsalicylic acid,

(d) the balance being inert filler. EXAMPLE 2 2. Fungicidal compositionscontaining an organic 35 fungicide in an amount from 5 to 95 togetherwith r F L Zznc Ethylen BIS Dzthzoca bamate (ZINEB) (a) 2 to 10% OIfatty alcohol p yg y ethers, the fatty alcohol having 12 to 18 carbonatoms and g 'g Evaluatlon numb" being etherified with up to 50 glycolresidues, and concentra- (b) 1 to 10% of fatty acid metal salts, thefatty acid g l gg' Sprawl 40 having 12 to 18 carbon atoms and the metalbeing a member selected from the group consisting of Normal formulation(commercially 0.05 5 15 9319mm, magneslum, Z1I1C and alumlruurn, and Iavailable i 29 (c) up to 10% of a solid organic acid, this acid being 88g 3 a member selected from the group consisting of a Inventivecombination 2a 38%; g 5% lower aliphatic dicarboxylic acid, a loweraliphatic Nonmated control 100 m0 hydroxy-carboxyllc acld and salicylicacid,

(d) the balance being inert filler. 3. Fun 'cidal com osition containinan or anic EXAMPLE 3 g p g g Zinc-Dimcthyl-Dithiocarbamate (ZIRAM)fungicide in an amount from 5 to 95 together with (a) 2 to 10% ofstearyl alcohol polyglycol ether being etherified with 5 to 25 glycolresidues, and (b) 1 to 10% of magnesium stearate, and (0) up to 10% of asolid organic acid, this acid being a member selected from the groupconsisting of a lower aliphatic dicarboxylic acid, a lower aliphatichydroxy-carboxylic acid and salicylic acid, (d) the balance being inertfiller. 4. Fungicidal compositions containing an organic fungicide in anamount from 5 to 95 together with (a) 2 to 10% of palmityl alcoholpolyglycol ether being etherified with 5 to 25 glycol residues, andcalcium palmityl polyglycol ether, and (b) 1 to 10% of magnesiumpahnitate, and (0) up to 10 of a solid organic acid, this acid being amember selected from the group consisting of a lower aliphaticdicarboxylic acid, a lower aliphatic hydroxy-carboxylic acid andsalicylic acid, (d) the balance being inert filler.

References Cited in the file of this patent UNITED STATES PATENTS

1. FUNGICIDAL COMPOSITIONS CONTAINING AN ORGANIC FUNGICIDE IN AN AMOUNTFROM 5 TO 95% TOGETHER WITH (A) 2 TO 10% OF A MEMBER SELECTED FROM THEGROUP CONSISTING OF PHENYL HYDROXY POLYGLYCOL E THERS, FATTY ACIDPOLYGLYCOL ESTERS AND FATTY ALCOHOL POLYGLYCOL ETHERS, THE FATTYALCOHOLS AND ACIDS HAVING 8 TO 25 CARBON ATOMS AND BEING ESTERIFIED WITHUP TO 50 GLYCOL RESIDUES, AND (B) 1 TO 10% FATTY ACID METAL SALTS, THEFATTY ACID HAVING 8 TO 25 CARBON ATOMS AND THE METAL BEING A MEMBERSELECTED FROM THE GROUP CONSISTING OF CALCIUM, MAGNESIUM, ZINC ANDALUMINIUM, AND (C) UP TO 10% OF A SOLID ORGANIC ACID, THIS ACID BEING AMEMBER SELECTED FROM THE GROUP CONSISTING OF A LOWER ALIPHATICDICARBOXYLIC ACID, A LOWER ALIPHATIC HYDROXY-CARBOXYLIC ACID ANDSALICYCLIC ACID, (D) THE BALANCE BEING INERT FILLER.